Process for the manufacture of color photographic images



Patented July 4, 1950 2,514,234 raocsss FOR THE MANUFACTURE or COLORPHOTOGRAPHIC IMAGES Bla Gaspar, Beverly Hills, Calif., assignor toChromogen, Incorporated, a corporation of Nevada No Drawing.Continuation 'of applicationSerial No. 541,282, June 20, 1944, which isadivision of application Serial No. 518,256, January 14, 1944, which inturn is a division of application Serial No. 351,907, August 8, 1940.This application October 14, 1947, Serial No..779,839. In Great BritainAugust 9, 1939 6 Claims.

The present application is a continuation of my application Serial No.541,282, filed June 20, 1944, now abandoned. Application Serial No.541,282 is a division of ,my application SerialNo. 518,256, filedJanuary 14, 1944, which inturn is a division of my Patent 2,361,541which relates to the production of dye images, from photo-'-' graphicsilver images by a process which comprises the synthesis of an azo dyein the exposed photographic emulsion layer.

In my prior United States Letters Patent No. 2,071,688, dated February23, 1937, I have described and claimed a method of producing colorphotographic images in which the photographic layer is subject totwotreatments, the first .treatment consisting inthe conversion of adye-forming substance into a dye and the second treatment consisting inthe local dye destruction at the required points in accordance withv myPatent 2,020,775. Thus, for example, a diazo compound is transformedinto an azo dye by coupling with a phenol; or a phenol or other azocoupler is transformed into an azo. dye by treating with adiazo-compound, the azo .dyes thus formed then being destroyed locally.

In my prior British Patent Specification No. 416,660, as well as inPatent 2,071,688 just mentioned, I have also described and. claimed analternativeprocess in which the first treatment consists in the localdestruction of the dye-forming substance, the :second treatment thenconsisting in the conversion of the remaining dyeforming substance intothe dye.v

If, for carryingout the processes referred to above, a layer is usedwhich contains either an azo coupler or a diazo compound but not both,the production of the dye image can be performed either by coupling witha diazo compound or coupling with an azo coupler, respectively, and thedestruction atthe image or non-image parts of the dye thereby obtained.v

If, however, the layer contains a diazotizable amino compound and an azocoupler, the process includes the step of diazotization, in addition tocoupling and destruction at the image or non image parts of either thediazo compound or the dye.

The present invention relates to the treatment of photographic layersthat either comprise both a diazotizable amino compound and a compound Ai .1 i'f i i that iscapable of coupling with diazo compounds or thatcomprise a compound'which is "both diazotizable and'then capable ofcoupling with itself. The operations'of diazotization, coupling anddestruction at the image parts are not carried out in three separatetreating steps butwith only two baths or even' with one single bath.

This simplification of the process is rendered possible by the presentinvention whiichconsists in imparting a triple function to the-treatingsolution or a dual function to one oftwo. treating solutions so that thesame treating solution is 'soin' which is distributed diffuselythroughout the layer is treated for about 5 minutes with a solution of250 ccs. of a 0.25-normal sulphuric acid and 1 cc. of a 0.1normal-sodium nitrite'solution.

The image is washed and immersed for about 5 minutes into a 2.5%thiocarbamide solution 7 containing 2% acetic acid which causes couplingoccur within the same solution. Aiter ab'out 10 to 20 minutes the silveris removed from the 3 dye image. The dye image can be improved bytreating the layer prior to the removal of the silver with a dyedestroying solution, such as a 5% hydrobromic acid solution.

Example: 3;f- A silver images-as used in Example 1 is treated witha'solution of cos. /z-n'ormal acetic acid containing 5% sodium chlorideand 0.1 cc. of a (Ll-normal sodium nitrite solution. After 20 minutesthe silver image isremoved by a cupric salt solution and fixinglifa'dyeimage is obtained.

Example 4.A silver image as used in Example 1 is treated with cos.- "ofa'solution of 0.25- normal hydrobromic acid to which 0.1 cc. of a0.1-normal sodium nitrite: solutionv have been.

diazonium compound at tl'i'e'points'of'thewsilver image. The layer isafter-treatedwith a' illz5- normal sodium carbonate to cause'ithedia'zotized T T.

The silver is removed, and

compound to couple. a reversed dye image obtained.

From the foregoing examples it will be seencarbonyl :fbi's' E8(4s4eaminmbenzamino),

mind) naphthol -fl) disulphonic acid-;(3 fi)1 Beilste'ins Handbuclr:der' Organischen: Chemi, th (26.2, 1933, Su'ppllNol; XIV, page'759;=F.formula may be used which" are distributed difi'usely throughouta layer.

The process of the present invention for the production of colorphotographic images is espe- "ceially useful for the manufacture ofmulti-color images in a plurality of layers. In the multiflayer-materialused-for thi process some -or all "fof. thelayers-may contain adyeiorm-ingi subfistance'capable of coupling withsitsel-i: or, some orfiiallbf the layers may contain'a diazotizable amino ompound-anda=compound that is capable of oupling Fwith diazo-compounds,.- a a claim?91; A process gimp-producing :a reversed photo- -'-graphic'dyestuffimage in a; layer comprising a silver image and adiazotizablefaminocompound distributed diffusely throughout said layer, which 1 comprisestreating said layerswith a. solution which causes said compound to be.diazotized and '1 then treating said layer 1 with; a single solution to-:.-"pro,duce a reversed dyestufiiimagewhich solution causes'coupling-of the diazotiaed compound to -"form- 'a dye in the presenceof. a' substance which e "isnon-destruetivewith respect .to...sa id.dye' but --reacts with saidsilver image-.to oxidize it andesubstantially simultaneously t0 f0,rrn a reducing substance.

2. A process for producing a reversed photoa compoiinw which fastl.Y;idyes a; silveri halide graphic dyestuff image in a layer comprising asilver image together with a diazotizable amino compound and a compoundcapable of coupling with diazo compounds, said compounds being uniformlydistributed throughout said layer,

which comprises treating said layer with a solution which causes saiddiazotizable amino compound to be diazotized and then treating saidlayer-with a single solution to produce a reversed dyestuff image whichsolution causes coupling of the diazo compound with the compound capableof coupling thereto, to form a dye in the presence of a substance whichis non-destructive with respect to said dye but reacts with said silverimage to oxidize it and substantially simultaneously to form a reducingsubstance. '3. A process. for producing a reversed photographic dyestuffimage in a layer comprisin a enter-"image and an amino compounddistributed diiiusely throughout said layer which is both dialzbtizableand then capable of coupling WithTitSBif to form a dye, which comprisestreating said layer with a solution which causes said emeteries esiized.end henir a ng s 25 ;layer;with ,a single solution'to produce areversed dyestufieimagelwhich solution causes the idi'aiotized,,compound to couplewit'hit'self'to form a dye invthepresenceof a substance which is nondestructive, withgre'spec't tcsaiddye but reacts with said 'ilyer image to gxidiz'e' it' and substan- -=ga h edyestuff.i 35. prising a silver in; c mpe e Re ets? specttotheemuls on w 4 7 throughout said layergwhich"comprises l-trating i lr wi h a sq ij ien w ich. ause Said 40 pound to iiedia zotiz gland thentr'eatiii'gfs .idlay- .er with a single 'splutionfto produce a reverseddyestufiimage, which solutionicau'ses'coupling of the diazotizedcompound" to form a dye in the presenceof asubstance whichisnon-destructive f. Witliffesp'ect tgj said dyeig'ut'reactswith said'silver image to. oxidize it ,andjsubs'tantially simultane- ..oiisly toio mareducing substance.

5. A process for-produc ng a reversed'photosg ereiasre m .imaee i a: x spr'isingfa'siiver, image tggether with a dia'z otizable amino compour dpos'ses'sing' dyeing propei ties tl 1;.,r spect to the em ilsion 1ayerand a compound"ca'fgable er coupling with uiaze'ecmpcu'rrss, saidcompounds ,being un'iiormly distributed throughout jsaid layen' whichcomprises treating said'layer with a solutiqn'fwhich au'ses said'diazotizablaamino compound to be diazotized and I ,then. treating said;-layer with a single solution to .produce a reversedjdyestufflimage,which solution 0 causes coupling'of the diazo compound with the compoundcapable of coupling? thereto tciorm a dye in the presence of a substancewhich is nondestructiyejwith respect to 'sa.id jdye but reacts with saidsilver image to oxidize it and'substantially simultaneously to" form areducing substance. V I

6..A process for producing'a' reversed photo- I graphic dyestufi imagein a layer comprising a silverirnage anda diazo compound distributeddiffusely throughout said layer, which comprises treating said layerwitha single solution to'prcduce. a reversed dyestufi image which solutioncausescouplmg of the diazo compound to form a dye in the presence of'asubstance whichis' nondestructive with respect to said dye but reacts 8with said silver image to oxidize it and substantially simultaneously toform a reducing substance.

BELA GASPAR.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date Lierg May 13, 1930 Number Number10 298,979 416,566

Great Britain Sept. 10, 1934

1. A PROCESS FOR PRODUCING A REVERSED PHOTOGRAPHIC DYESTUFF IMAGE IN ALAYER COMPRISING A SILVER IMAGE AND A DIAZOTIZABLE AMINO COMPOUNDDISTRIBUTED DIFFUSELY THROUGHOUT SAID LAYER, WHICH COMPRISES TREATINGSAID LAYER WITH A SOLUTION WHICH CAUSES SAID COMPOUND TO BE DIAZOTIZEDAND THEN TREATING SAID LAYER WITH A SINGLE SOLUTION TO PRODUCE AREVERSED DYESTUFF IMAGE WHICH SOLUTION CAUSES COUPLING OF THE DIAZOTIZEDCOMPOUND TO FORM A DYE IN THE PRESENCE OF A SUBSTANCE WHICH ISNON-DESTRUCTIVE WITH RESPECT TO SAID DYE BUT REACTS WITH SAID SILVERIMAGE TO OXIDIZE IT AND SUBSTANTIALLY SIMULTANEOUSLY TO FORM A REDUCINGSUBSTANCE.